EP1310524A1 - Thermoplastic elastomer composition, formed article of the same and composite formed article of the same - Google Patents
Thermoplastic elastomer composition, formed article of the same and composite formed article of the same Download PDFInfo
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- EP1310524A1 EP1310524A1 EP02356169A EP02356169A EP1310524A1 EP 1310524 A1 EP1310524 A1 EP 1310524A1 EP 02356169 A EP02356169 A EP 02356169A EP 02356169 A EP02356169 A EP 02356169A EP 1310524 A1 EP1310524 A1 EP 1310524A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- This invention relates to a thermoplastic elastomer composition, and formed article and composite formed article of the same; more particularly to a thermoplastic elastomer composition excellent in softness, permanent compression set (both short- and long-term) and moldability, and controlled in bleed-out of the softening agent, and formed article and composite formed article of the same.
- thermoplastic elastomers which are soft materials with rubber elasticity, need no vulcanization, and are as moldable and recyclable as thermoplastic resins have been massively going into various areas, such as automobile parts, home electric appliances, wire coatings, medical equipment parts, footwear and miscellaneous goods.
- thermoplastic elastomers polystyrene-based ones, e.g., styrene-butadiene block copolymer (SBS) and styrene-isoprene block copolymer (SIS) as aromatic vinyl compound and conjugated diene compound block copolymers are highly soft, have good rubber elasticity at normal temperature and give highly moldable thermoplastic elastomer compositions. As such, they are massively used as substitutes for vulcanized rubber.
- SBS styrene-butadiene block copolymer
- SIS styrene-isoprene block copolymer
- the elastomer composition of styrene and conjugated diene block copolymer, as one type of the above elastomers, whose intramolecular double bonds are hydrogenated is more massively used as the one having improved resistance to aging under heat (thermal stability) and to weather.
- thermoplastic elastomer composition containing the hydrogenated block copolymer still involves some problems in rubber characteristics, e.g., resistance to oil, deformation rate (permanent compression set) under heated and pressurized conditions and rubber elasticity at high temperature.
- the compositions containing a hydrogenated derivative of the above block copolymer have been crosslinked to improve the above characteristics, and these crosslinked compounds are disclosed by, e.g., Japanese Patent Laid-open Publication Nos.S59-6236 and S63-57662, and Japanese Patent Publication Nos. H3-49927, H3-11291 and H6-13628.
- the crosslinked compositions of hydrogenated block copolymers disclosed by the above patent publications still have problems of insufficient permanent compression set at high temperature, in particular 100°C, and tending to lose mechanical strength. Therefore, they are still short of the performance level which has been required in the areas for vulcanized rubber, as matters now stand. Moreover, they involve many moldability-related problems, e.g., low melt tension of the extruded article at high temperature, deteriorating its ability of keeping its shape, and extended molding cycles of injection-molded article.
- compositions disclosed by the above patent publications has a Shore A hardness of 40 or more, and is softened by increasing softening agent content.
- this causes practical problems, e.g., sticky surfaces of the molded article and bleed-out of the softening agent in the presence of stress under heating, as matters now stand.
- thermoplastic elastomer composition excellent in softness, permanent compression set (both short- and long-term), and controlled in bleed-out of the softening agent. It is another object of the present invention to provide a formed article and composite formed article of the above thermoplastic elastomer composition.
- thermoplastic elastomer composition excellent in softness, permanent compression set and moldability, and controlled in bleed-out of the softening agent can be obtained by melting and kneading a specific, hydrogenated polystyrene-based elastomer with a thermoplastic resin of low melting point and melt viscosity, reaching the present invention.
- the first invention is a thermoplastic elastomer composition containing:
- the second invention is the thermoplastic elastomer composition of the first invention which further contains (d) 0.01 to 3 parts by weight of an organic peroxide.
- the third invention is the thermoplastic elastomer composition of the second invention which further contains (e) 0.1 to 10 parts by weight of an ester-based crosslinking aid.
- the fourth invention is the thermoplastic elastomer composition of one of the first to third inventions which further contains (f) 0.1 to 25 parts by weight of a peroxide-decomposed type polyolefin resin.
- the fifth invention is a formed article composed of the thermoplastic elastomer composition containing:
- the sixth invention is an elastic part composed of the formed article of the fifth invention for medical, food or bubble jet printer purpose.
- the seventh invention is a thermal adhesiveness formed composite article composed of the formed article of the fifth invention and a formed article of polypropylene-based resin thermal adhered to each other under heating.
- the eighth invention is an elastic part composed of the thermal adhesiveness formed article of the seventh invention for medical, food or bubble jet printer purpose.
- the ninth invention is a formed article composed of the thermoplastic elastomer composition containing:
- the tenth invention is an elastic part composed of the formed article of the ninth invention for medical, food or bubble jet printer purpose.
- the 11 th invention is a thermal adhesiveness formed composite article composed of the formed article of the ninth invention and a formed article of polypropylene-based resin thermal adhered to each other under heating.
- the 12 th invention is an elastic part composed of the thermal adhesiveness formed article of the 11 th invention for medical, food or bubble jet printer purpose.
- thermoplastic elastomer composition of the present invention is described in more detail for its components, method of production, applications and so on.
- thermoplastic elastomer composition 1.
- Components of the thermoplastic elastomer composition 1.
- At least one hydrogenated block copolymer selected from the group consisting of: (a-1) a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of at least 2 polymer blocks A mainly based on an aromatic vinyl compound and at least one polymer block B mainly based on a conjugated diene compound, and (a-2) a hydrogenated block copolymer obtained by hydrogenating a block copolymer based on a conjugated diene compound as component (a)
- the hydrogenated block copolymer (a-1) for the thermoplastic elastomer composition of the present invention obtained by hydrogenating a block copolymer composed of at least 2 polymer blocks A mainly based on an aromatic vinyl compound and at least one polymer block B mainly based on a conjugated diene compound, is a polymer obtained by hydrogenating a block copolymer composed of at least 2 polymer blocks A mainly based on an aromatic vinyl compound and at least one polymer block B mainly based on a conjugated diene compound.
- the examples of the hydrogenated block copolymer (a-1) are the hydrogenated block copolymers of an aromatic vinyl compound and conjugated diene compound, having the structure of A-B-A, B-A-B-A or A-B-A-B-A.
- the polymer block A mainly based on an aromatic vinyl compound may be composed only of the aromatic vinyl compound or a copolymer of the aromatic vinyl compound and a conjugated diene compound, accounting for less than 50% by weight.
- the polymer block B mainly based on a conjugated diene compound may be composed only of the conjugated diene compound or a copolymer of the conjugated diene compound and an aromatic vinyl compound, accounting for less than 50% by weight.
- the polymer block B mainly based on a conjugated diene compound for the hydrogenated block polymer component (a-1), obtained by hydrogenating a block copolymer composed of at least 2 polymer blocks A mainly based on an aromatic vinyl compound and at least one polymer block B mainly based on a conjugated diene compound, is not limited in extent of hydrogenation. However, it is preferably 50% or more, more preferably 55% or more, still more preferably 60% or more. Its micro structure is also not limited.
- the 1,2-micro-structure preferably accounts for 20 to 50% by weight, particularly preferably 25 to 45% by weight, in the polybutadiene block. The 1,2-bond may be selectively hydrogenated for the block.
- the block B is composed of a mixture of isoprene and butadiene, the 1,2-micro-structure preferably accounts for 50% or less, more preferably 25% or less, still more preferably 15% or less.
- the block B is composed of isoprene as the single component, preferably 70 to 100% by weight of isoprene in the polyisoprene block has the 1,4-micro-structure, and preferably 90% or more of the aliphatic double bond derived from isoprene is hydrogenated.
- the above hydrogenated compound can be preferably used, as required, for the purposes.
- the amount of the polymer block A present in the component (a-1) is 5 to 70 % by weight, based on the weight of the component (a-1). Further, it is preferred that the total weight-average molecular weight of the component (a-1) is 50,000 to 550,000.
- component (a-1) examples include styrene-ethylene/butene-styrene copolymer (SEBS), styrene-ethylene/propylene-styrene copolymer (SEPS), styrene-ethylene/ethylene/propylene-styrene copolymer (SEEPS), and styrene-butadiene/butylene-styrene copolymer (partially hydrogenated styrene-butadiene-styrene copolymer, SBBS).
- SEBS styrene-ethylene/butene-styrene copolymer
- SEPS styrene-ethylene/propylene-styrene copolymer
- SEEPS styrene-ethylene/ethylene/propylene-styrene copolymer
- SBBS styrene-butadiene/butylene-styrene copolymer
- a number of methods have been proposed for producing the block copolymer, obtained by hydrogenating a block copolymer composed of at least 2 polymer blocks A mainly based on an aromatic vinyl compound and at least one polymer block B mainly based on a conjugated diene compound.
- One of the representative methods involves block polymerization effected in an inert medium in the presence of a lithium or Ziegler catalyst, as disclosed by Japanese Patent Publication No.S40-23798.
- the resultant block copolymer can be hydrogenated in an inert medium in the presence of a hydrogenation catalyst by a known method.
- the hydrogenated block copolymers of a conjugated diene compound useful for the present invention as the (a-2) component include a block copolymer (CEBC) composed of a crystalline ethylene block and non-crystalline ethylene-butene block obtained by hydrogenating a block copolymer of butadiene.
- CEBC block copolymer
- the hydrogenated block copolymers of a conjugated diene compound may be used either individually or in combination.
- the non-aromatic-based softening agents for rubber as the component (b) for the thermoplastic elastomer composition of the present invention include a non-aromatic-based mineral oil, and liquid or low-molecular-weight synthetic agent.
- the softening agents of mineral oil for rubber are generally a mixture of an aromatic ring, naphthenic ring and paraffin chain compounds. They are distinguished from each other by the paraffin-, naphthene- and aromatic-based ones, when carbons in the paraffin chains account for 50% or more of the total carbons, those in the naphthene rings for 30 to 40%, and the aromatic ones for 30% or more, respectively.
- the softening agents of mineral oil for rubber useful as the component (b) for the present invention are paraffin- or naphthene-based ones. Use of an aromatic-based softening agent is undesirable, because it will make the component (a) soluble to retard the crosslinking reactions with the result that properties of the resultant composition may not be improved.
- the component (b) for the present invention is preferably a paraffin-based one, and the one having a lower aromatic ring content is more preferable.
- liquid or low-molecular-weight synthetic softening agents include a polybutene, a hydrogenated polybutene and a low-molecular-weight polyisobutylene. Among these, a polybutene and a hydrogenated polybutene are preferred.
- the non-aromatic-based softening agent for rubber preferably has a kinematic viscosity of 20 to 50,000cSt at 37.8°C and 5 to 1,500cSt at 100°C, pour point of -10 to -15°C, and flash point (COC) of 170 to 300°C. Moreover, it preferably has a weight-average molecular weight of 100 to 2,000.
- the component (b) is incorporated, when the component (a-1) is used as the component (a), at 30 to 150 parts by weight per 100 parts by weight of the component (a-1), preferably 50 to 120 parts by weight.
- the resultant thermoplastic elastomer composition may have deteriorated moldability, excessively high hardness and deteriorated softness with the result that the composition may not give the rubber-touch product.
- the resultant thermoplastic elastomer composition is liable to suffer bleed-out of the softening agent, and the formed article delamination and/or peeling of the components, deformation and flow marks on the surfaces.
- the component (b) is incorporated, when the component (a-2) is used as the component (a), at 30 to 170 parts by weight per 100 parts by weight of the component (a-2), preferably 50 to 160 parts by weight.
- the resultant thermoplastic elastomer composition may have deteriorated moldability, excessively high hardness and deteriorated softness with the result that the composition may not give the rubber-touch product.
- the resultant thermoplastic elastomer composition is liable to suffer bleed-out of the softening agent, and the formed article delamination and/or peeling of the components, deformation and flow marks on the surfaces.
- the petroleum hydrocarbon resin component (c) for the thermoplastic elastomer composition of the present invention has the effects of accelerating dispersion of the rubber in the resultant thermoplastic elastomer composition, improving outer appearances of the formed article, and adjusting hardness and shrinkage.
- Examples of such petroleum hydrocarbon resins include an aliphatic petroleum resin produced mainly from C 5 fraction by-produced in the steam cracking of petroleum; an aromatic petroleum resin produced mainly from C 9 fraction; and a C 5 C 9 copolymer obtained by copolymerizing the above-mentioned C 5 fraction with C 9 fraction.
- the type of the petroleum hydrocarbon resin is a copolymer having aromatic groups.
- the component (c) has a softening point of 80 to 170°C, preferably 110 to 160°C. At a softening point of the component (c) out of the above range, the resultant elastomer composition may have deteriorated balances among softness, permanent compression set and moldability.
- the temperature at which the component (c) exhibits a melt viscosity of 10 poise is 120 to 250°C, preferably150 to 240°C. When this temperature is lower than 120°C, the resultant elastomer composition may have deteriorated rubber elasticity. When this temperature is higher than 250°C, the resultant elastomer composition may have deteriorated moldability.
- the preferable examples of commercially available resins usable as the component (c) include aromatic group-containing resins, such as Endex 155 (a copolymer produced using an aromatic monomer, Eastman Chemical) and Kristalex 5140 (a copolymer of ⁇ -methylstyrene with styrene, Eastman Chemical).
- aromatic group-containing resins such as Endex 155 (a copolymer produced using an aromatic monomer, Eastman Chemical) and Kristalex 5140 (a copolymer of ⁇ -methylstyrene with styrene, Eastman Chemical).
- the component (c) is incorporated at 3 to 100 parts by weight per 100 parts by weight of the component (a), preferably 10 to 50 parts by weight.
- the resultant elastomer composition may have deteriorated moldability, and the formed article is liable to suffer delamination and/or peeling of the components, deformation and flow marks on the surfaces.
- the resultant elastomer composition may also have deteriorated moldability, excessively high hardness and deteriorated softness with the result that the composition may not give the rubber-touch product.
- thermoplastic elastomer composition of the present invention may be incorporated with the organic peroxide component (d), as required.
- the organic peroxide component (d) works to generate the radicals which are reacted with each other in a chain reaction manner to crosslink the component (a).
- Examples of compounds useful for the component (d) include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butyl peroxy)hexane, 2,5-dimethyl-2,5-di-(tert-butyl peroxy)hexyne-3, 1,3-bis(tert-butyl peroxyisopropyl)benzene, 1,1-bis(tert-butyl peroxy)-3,3,5-trimethyl cyclohexane, n-butyl-4,4-bis(tert-butyl peroxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert
- 2,5-dimethyl-2,5-di-(tert-butyl peroxy)hexane and 2,5-dimethyl-2,5-di-(tert-butyl peroxy)hexyne-3 are particularly preferable for their characteristics related to odor, coloring and scorch safety.
- the component (d) When it is used, the component (d) is incorporated at 0.01 to 3 parts by weight per 100 parts by weight of the component (a), preferably 0.05 to 1.0 parts by weight. At below 0.01 parts by weight, the resultant thermoplastic elastomer composition may have insufficient resistance to heat and mechanical strength, because of insufficient extent of crosslinking. At above 3 parts by weight, on the other hand, the resultant thermoplastic elastomer composition may have deteriorated moldability.
- thermoplastic elastomer composition of the present invention may be incorporated with an ester-based crosslinking aid as the component (e), as required.
- the component (e) may be incorporated during the crosslinking step in the presence of the organic peroxide component(d) as the component (e) in the production of the thermoplastic elastomer composition, for the uniform and efficient crosslinking reactions.
- it can adequately crosslink the non-aromatic-based softening agent for rubber, in particular low-molecular-weight paraffin-based oil or the like, to control its bleed-out from the thermoplastic elastomer composition.
- the compounds useful for the component (e) include multi-functional methacrylate compounds, e.g., triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate having 9 to 14 recurring units of ethylene glycol, trimethylol propane trimethacrylate, allylmethacrylate, 2-methyl-1,8-octanediol dimethacrylate and 1,9-nonanediol dimethacrylate; multi-functional acrylate compounds, e.g., polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate and propylene glycol diacrylate; and multi-functional vinyl compounds, e.g., vinyl butylate and vinyl stearate.
- multi-functional methacrylate compounds e.g.,
- crosslinking aids the multifunctional acrylate and methacrylate compounds are more preferable, and triethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate are still more preferable. These compounds are easily handled, function to solubilize the organic peroxide and hence as the dispersion aid for the peroxide, and promote the uniform and efficient crosslinking reactions under heating, to give the thermoplastic elastomer composition of well-balanced hardness and rubber elasticity.
- the component (e) is incorporated, when it is used, preferably at 0.1 to 10 parts by weight per 100 parts by weight of the component (a), more preferably 0.1 to 3 parts by weight. At above 10 parts by weight, it may no longer exhibit its effect, because the resultant thermoplastic elastomer has a decreased extent of crosslinking due to the self-polymerization.
- thermoplastic elastomer composition of the present invention may be incorporated with a peroxide-decomposed type polyolefin resin as the component (f), as required.
- the component (f) can significantly improve ability of thermal adhering of the formed article of the resultant thermoplastic elastomer with a formed article of peroxide-decomposed type polyolefin resin.
- the component (f) is composed of an olefin-based polymer or copolymer, thermally decomposed under heating in the presence of a peroxide to lose its molecular weight and have increased fluidity while being molten.
- the compounds useful for the component (f) include isotactic polypropylene or copolymer of propylene with another ⁇ -olefin compound, e.g., ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene.
- the homopolymer portion of the above olefin-based copolymer preferably has a DSC-determined melting point (Tm) of 150 to 167°C, and ⁇ Hm of 25 to 83mJ/mg. Degree of crystallinity can be estimated from the DSC-determined Tm and ⁇ Hm.
- Tm DSC-determined melting point
- ⁇ Hm 25 to 83mJ/mg.
- Degree of crystallinity can be estimated from the DSC-determined Tm and ⁇ Hm.
- the resultant thermoplastic elastomer composition may no longer exhibit improved resistance to oil and rubber elasticity at 100°C or higher, when the homopolymer portion has the Tm or ⁇ Hm out of the above range.
- the component (f) preferably has a melt flow rate (MFR, determined at 230°C in accordance with ASTM D-1238) of 0.1 to 200g/10 minutes, more preferably 0.5 to 100g/10minutes.
- MFR melt flow rate
- the resultant thermoplastic elastomer composition may have deteriorated moldability.
- it may have deteriorated rubber elasticity.
- the component (f) is incorporated, when it is used, preferably at 0.1 to 25 parts by weight per 100 parts by weight of the component (a), more preferably 1 to 20 parts by weight. At above 25 parts by weight, the resultant thermoplastic elastomer may have deteriorated softness and rubber elasticity.
- thermoplastic elastomer composition of the present invention may be incorporated with one or more types of additives, in addition to the above-described components, as required.
- additives include various types of blocking inhibitor, sealing improver, heat stabilizer, antioxidant, light stabilizer, ultraviolet ray absorber, lubricant, nucleating agent and colorant.
- antioxidants useful for the present invention include phenol-based ones, e.g., 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butyl phenol, 2,4-dimethyl-6-tert-butyl phenol, 4,4-dihydroxydiphenyl and tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane; phosphate-based ones; and thioether-based ones. Of these, phenol- and phosphate-based ones are particularly preferable.
- the antioxidant is incorporated preferably at 0 to 3.0 parts by weight per 100 parts by weight of the components (a) to (f) totaled, particularly preferably 0.1 to 1.0 parts by weight.
- thermoplastic elastomer composition 1.
- thermoplastic elastomer composition of the present invention can be produced by kneading the components (a) to (c), and, as required, optional components (d) to (g), which may be incorporated simultaneously or in an optional sequence.
- the melting/kneading method is not limited, and the known method may be used.
- these components may be molten and kneaded by a single screw extruder, twin screw extruder, roll, Banbury mixer, or various types of kneader.
- the melting and kneading steps may be effected continuously by, e.g., a twin screw extruder of adequate L/D ratio, Banbury mixer or kneader.
- the preferable melt kneading temperature is 160 to 220°C.
- thermoplastic elastomer composition
- thermoplastic elastomer composition of the present invention has adequate softness and permanent compression set, in particular excellent compression set at 70°C or lower, and causes no environmental pollution, because the formed article suffers only a limited extent of bleed-out of the softening agent even when exposed to an excessive stress-induced deformation or load.
- thermoplastic elastomer composition of the present invention can go into various areas, when formed into a shape, e.g., sealing parts for medical and food purposes, electric appliance parts, bottle cap packings, sealing parts for automobiles, and multi-color sealing parts formed with a polyolefin or hard thermoplastic elastomer. It is particularly useful for sealing parts of ink in a bubble jet printer or the like.
- thermoplastic elastomer composition of the present invention is excellent in ability of thermal adhering with a polyolefin resin, in particular polypropylene-based resin. Therefore, the formed article of the thermoplastic elastomer composition can be easily thermal adhered with a formed article of polypropylene-based resin, to form the thermal adhesiveness composite article.
- thermal adhesiveness composite articles include sealing parts for medical and food purposes, electric appliance parts, bottle cap packings, sealing parts for automobiles, and multi-color sealing parts.
- the composite articles are particularly useful for sealing parts of ink in a bubble jet printer or the like.
- composition The properties of each composition were determined by the following methods.
- the polypropylene resin plate 3 150mm long, 25mm wide and 4mm thick, was prepared by injection molding under the following injection conditions.
- the resin for the test plate is described below.
- Polypropylene resin PP-BC8 (Japan Polychem), Degree of crystallinity: Tm 166°C, ⁇ Hm: 82mJ/mg, MFR: 1.8g/10 minutes (The injection molding conditions were those recommended by the resin maker)
- the paper 4 was put on part of the polypropylene resin 3 by a double-faced tape. It was inserted in a mold, and the thermoplastic elastomer composition was injected into the mold under the following conditions, to prepare the test piece of the polypropylene resin plate 3 and thermoplastic elastomer composition plate 2 thermal adhesiveness to each other at the area A.
- Injection molder FS-120 Nei Plastic Industrial Forming temperature 180 to 220°C Mold temperature 40°C Injection speed 55mm/second Injection pressure 1,400kg/cm 2 Dwelling pressure 0kg/cm 2 Injection time 6 seconds Cooling time 45 seconds
- test piece thus prepared was tested by the 180 degree peel back strength test, where the thermoplastic elastomer composition plate 2 was folded as shown in Figure 3, and the end of the plate 2 and that of the plate 3 were pulled in the arrowed directions, to determine the 180 degree peel back strength according to the following standards:
- Tables 1 to 4 The components shown in Tables 1 to 4 were molten/kneaded into pellets by a twine screw extruder (L/D: 47) at 180°C and 350rpm as the screw speed. The resultant pellets were injection-molded to prepare the test pieces which were tested for various characteristics. The results are given in Tables 1 to 4.
- thermoplastic elastomer compositions prepared in EXAMPLES 1 to 8 was the composition of the present invention. It had good properties, whether or not it contained the optional components (d) to (g).
- the thermoplastic elastomer composition prepared in EXAMPLE 4 was particularly excellent in properties related to resealing and safety for medical equipment parts (Food Hygiene Act; standards for foods and additives (Notification No.370 of the Japanese Ministry of Health and Welfare issued in 1959), standards for tools and container wrappings of synthetic resin mainly composed of polystyrene (Notification No.20 of the Japanese Ministry of Health and Welfare issued in 1982)).
- thermoplastic elastomer composition of the present invention prepared by incorporating PP in the composition prepared in each of EXAMPLES 1 to 4 at 5 parts by weight per 100 parts by weight of SEPS, showed good ability of thermal adhering with a formed article of PP.
- DYNARON 6100P JSR Corp.
- JSR Corp. is a block copolymer (CEBC) composed of the crystalline ethylene block and non-crystalline ethylene-butene block, which is obtained by hydrogenating a block copolymer of butadiene.
- CEBC block copolymer
- the composition prepared in each of EXAMPLES 5 to 8 contained PP and showed good thermal adhering with a formed article of PP.
- the composition prepared in each of COMPARATIVE EXAMPLES 1 to 2 and 9 to 10 contained the component (b) at a content out of the range for the present invention.
- the resulting thermoplastic elastomer composition had an excessively high hardness, lost softness, could not give the product of rubber touch, and had deteriorated injection moldability.
- the component (b) was contained at a content above the range, the resulting thermoplastic elastomer composition suffered notable bleeding, and had deteriorated resistance to tacking and deteriorated injection moldability (due to occurrence of remarkable gas burn mark, stick in mold and mold contamination).
- the composition prepared in each of COMPARATIVE EXAMPLES 3 to 4 and 11 to 12 contained the component (c-1) at a content out of the range for the present invention.
- the component (c-1) was contained at a content below the range for the present invention, the resulting thermoplastic elastomer composition had deteriorated injection moldability.
- the component (c-1) was contained at a content above the range, the resulting thermoplastic elastomer composition lost softness, and had deteriorated rubber elasticity and deteriorated injection moldability (due to occurrence of remarkable sink mark, flash and stringiness).
- the composition prepared in each of COMPARATIVE EXAMPLES 5 to 6 and 13 to 14 contained the component (b) at a content out of the range for the present invention.
- the component (b) was contained at a content below the range for the present invention, the resulting thermoplastic elastomer composition had an excessively high hardness, lost softness, could not give the product of rubber touch, and had deteriorated injection moldability.
- the component (b) was contained at a content above the range, the resulting thermoplastic elastomer composition suffered notable bleeding, had deteriorated degree of non-tackiness and injection moldability, and was insufficient in safety for medical equipment parts.
- the composition prepared in each of COMPARATIVE EXAMPLES 7 to 8 and 15 to 16 contained the component (c-1) at a content out of the range for the present invention.
- the component (c-1) was contained at a content below the range for the present invention, the resulting thermoplastic elastomer composition had deteriorated injection moldability.
- the component (c-1) was contained at a content above the range, the resulting thermoplastic elastomer composition lost softness, had deteriorated rubber elasticity and injection moldability, and was insufficient in safety for medical equipment parts.
- thermoplastic elastomer composition of the present invention is controlled in bleed-out of the softening agent, excellent in softness, permanent compression set, and the formed article of the thermoplastic elastomer composition of the present invention causes no pollution of the ambient environments and can be used as excellent parts for various purposes, in particular it causes no deterioration of ink when used for the elastic part or the like for bubble jet printer, causes no deterioration of the content in a bottle when used for the bottle cap packing or the like, and causes no bleeding when used for the formed composite articles, e.g., multi-color sealing parts or the like formed with a polyolefin or hard thermoplastic elastomer, which articles are represented by the sealing parts for medical purposes, food purposes and electric appliances.
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Abstract
Description
- This invention relates to a thermoplastic elastomer composition, and formed article and composite formed article of the same; more particularly to a thermoplastic elastomer composition excellent in softness, permanent compression set (both short- and long-term) and moldability, and controlled in bleed-out of the softening agent, and formed article and composite formed article of the same.
- Recently, thermoplastic elastomers which are soft materials with rubber elasticity, need no vulcanization, and are as moldable and recyclable as thermoplastic resins have been massively going into various areas, such as automobile parts, home electric appliances, wire coatings, medical equipment parts, footwear and miscellaneous goods.
- Of thermoplastic elastomers, polystyrene-based ones, e.g., styrene-butadiene block copolymer (SBS) and styrene-isoprene block copolymer (SIS) as aromatic vinyl compound and conjugated diene compound block copolymers are highly soft, have good rubber elasticity at normal temperature and give highly moldable thermoplastic elastomer compositions. As such, they are massively used as substitutes for vulcanized rubber.
- The elastomer composition of styrene and conjugated diene block copolymer, as one type of the above elastomers, whose intramolecular double bonds are hydrogenated is more massively used as the one having improved resistance to aging under heat (thermal stability) and to weather.
- However, the thermoplastic elastomer composition containing the hydrogenated block copolymer still involves some problems in rubber characteristics, e.g., resistance to oil, deformation rate (permanent compression set) under heated and pressurized conditions and rubber elasticity at high temperature. The compositions containing a hydrogenated derivative of the above block copolymer have been crosslinked to improve the above characteristics, and these crosslinked compounds are disclosed by, e.g., Japanese Patent Laid-open Publication Nos.S59-6236 and S63-57662, and Japanese Patent Publication Nos. H3-49927, H3-11291 and H6-13628.
- However, the crosslinked compositions of hydrogenated block copolymers disclosed by the above patent publications still have problems of insufficient permanent compression set at high temperature, in particular 100°C, and tending to lose mechanical strength. Therefore, they are still short of the performance level which has been required in the areas for vulcanized rubber, as matters now stand. Moreover, they involve many moldability-related problems, e.g., low melt tension of the extruded article at high temperature, deteriorating its ability of keeping its shape, and extended molding cycles of injection-molded article.
- Each of the compositions disclosed by the above patent publications has a Shore A hardness of 40 or more, and is softened by increasing softening agent content. However, this causes practical problems, e.g., sticky surfaces of the molded article and bleed-out of the softening agent in the presence of stress under heating, as matters now stand.
- It is an object of the present invention to provide a thermoplastic elastomer composition excellent in softness, permanent compression set (both short- and long-term), and controlled in bleed-out of the softening agent. It is another object of the present invention to provide a formed article and composite formed article of the above thermoplastic elastomer composition.
- The inventors of the present invention have found, after having extensively studied to achieve the above objects, that a thermoplastic elastomer composition excellent in softness, permanent compression set and moldability, and controlled in bleed-out of the softening agent can be obtained by melting and kneading a specific, hydrogenated polystyrene-based elastomer with a thermoplastic resin of low melting point and melt viscosity, reaching the present invention.
- The first invention is a thermoplastic elastomer composition containing:
- (a) 100 parts by weight of at least one hydrogenated block copolymer selected
from the group consisting of:
- (a-1) a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of at least 2 polymer blocks A mainly based on an aromatic vinyl compound and at least one polymer block B mainly based on a conjugated diene compound, and
- (a-2) a hydrogenated block copolymer obtained by hydrogenating a block copolymer based on a conjugated diene compound;
- (b) 30 to 150 parts by weight of a non-aromatic-based softening agent for rubber; and
- (c) 3 to 100 parts by weight of a petroleum hydrocarbon resin having a softening point of 80 to 170°C, and a temperature at which the resin exhibits a melt viscosity of 10 poise is 120 to 250°C.
-
- The second invention is the thermoplastic elastomer composition of the first invention which further contains (d) 0.01 to 3 parts by weight of an organic peroxide.
- The third invention is the thermoplastic elastomer composition of the second invention which further contains (e) 0.1 to 10 parts by weight of an ester-based crosslinking aid.
- The fourth invention is the thermoplastic elastomer composition of one of the first to third inventions which further contains (f) 0.1 to 25 parts by weight of a peroxide-decomposed type polyolefin resin.
- The fifth invention is a formed article composed of the thermoplastic elastomer composition containing:
- (a) 100 parts by weight of at least one hydrogenated block copolymer selected
from the group consisting of:
- (a-1) a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of at least 2 polymer blocks A mainly based on an aromatic vinyl compound and at least one polymer block B mainly based on a conjugated diene compound, and
- (a-2) a hydrogenated block copolymer obtained by hydrogenating a block copolymer based on a conjugated diene compound;
- (b) 30 to 150 parts by weight of a non-aromatic-based softening agent for rubber; and
- (c) 3 to 100 parts by weight of a petroleum hydrocarbon resin having a softening point of 80 to 170°C, and a temperature at which said resin exhibits a melt viscosity of 10 poise is 120 to 250°C.
-
- The sixth invention is an elastic part composed of the formed article of the fifth invention for medical, food or bubble jet printer purpose.
- The seventh invention is a thermal adhesiveness formed composite article composed of the formed article of the fifth invention and a formed article of polypropylene-based resin thermal adhered to each other under heating.
- The eighth invention is an elastic part composed of the thermal adhesiveness formed article of the seventh invention for medical, food or bubble jet printer purpose.
- The ninth invention is a formed article composed of the thermoplastic elastomer composition containing:
- (a) 100 parts by weight of at least one hydrogenated block copolymer selected
from the group consisting of:
- (a-1) a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of at least 2 polymer blocks A mainly based on an aromatic vinyl compound and at least one polymer block B mainly based on a conjugated diene compound, and
- (a-2) a hydrogenated block copolymer obtained by hydrogenating a block copolymer based on a conjugated diene compound;
- (b) 30 to 150 parts by weight of a non-aromatic-based softening agent for rubber;
- (c) 3 to 100 parts by weight of a petroleum hydrocarbon resin having a softening point of 80 to 170°C, and a temperature at which said resin exhibits a melt viscosity of 10 poise is 120 to 250°C;and
- (d) 0.01 to 3 parts by weight of an organic peroxide.
-
- The tenth invention is an elastic part composed of the formed article of the ninth invention for medical, food or bubble jet printer purpose.
- The 11th invention is a thermal adhesiveness formed composite article composed of the formed article of the ninth invention and a formed article of polypropylene-based resin thermal adhered to each other under heating.
- The 12th invention is an elastic part composed of the thermal adhesiveness formed article of the 11th invention for medical, food or bubble jet printer purpose.
-
- Figure 1 is a front view of the test piece for determining peel back strength.
- Figure 2 is a cross-sectional view of the test piece for determining peel back strength.
- Figure 3 is a cross-sectional view of the test piece for explaining the method of determining peel back strength.
-
-
- 1
- Test piece
- 2
- Plate of the thermoplastic elastomer composition
- 3
- Plate of a polypropylene resin
- 4
- Paper
- A
- Thermal adhesiveness area
- The thermoplastic elastomer composition of the present invention is described in more detail for its components, method of production, applications and so on.
- The hydrogenated block copolymer (a-1) for the thermoplastic elastomer composition of the present invention, obtained by hydrogenating a block copolymer composed of at least 2 polymer blocks A mainly based on an aromatic vinyl compound and at least one polymer block B mainly based on a conjugated diene compound, is a polymer obtained by hydrogenating a block copolymer composed of at least 2 polymer blocks A mainly based on an aromatic vinyl compound and at least one polymer block B mainly based on a conjugated diene compound. The examples of the hydrogenated block copolymer (a-1) are the hydrogenated block copolymers of an aromatic vinyl compound and conjugated diene compound, having the structure of A-B-A, B-A-B-A or A-B-A-B-A.
- The polymer block A mainly based on an aromatic vinyl compound may be composed only of the aromatic vinyl compound or a copolymer of the aromatic vinyl compound and a conjugated diene compound, accounting for less than 50% by weight.
- The polymer block B mainly based on a conjugated diene compound may be composed only of the conjugated diene compound or a copolymer of the conjugated diene compound and an aromatic vinyl compound, accounting for less than 50% by weight.
- The polymer block B mainly based on a conjugated diene compound for the hydrogenated block polymer component (a-1), obtained by hydrogenating a block copolymer composed of at least 2 polymer blocks A mainly based on an aromatic vinyl compound and at least one polymer block B mainly based on a conjugated diene compound, is not limited in extent of hydrogenation. However, it is preferably 50% or more, more preferably 55% or more, still more preferably 60% or more. Its micro structure is also not limited.
When the block B is composed only of butadiene, for example, the 1,2-micro-structure preferably accounts for 20 to 50% by weight, particularly preferably 25 to 45% by weight, in the polybutadiene block. The 1,2-bond may be selectively hydrogenated for the block. When the block B is composed of a mixture of isoprene and butadiene, the 1,2-micro-structure preferably accounts for 50% or less, more preferably 25% or less, still more preferably 15% or less. - When the block B is composed of isoprene as the single component, preferably 70 to 100% by weight of isoprene in the polyisoprene block has the 1,4-micro-structure, and preferably 90% or more of the aliphatic double bond derived from isoprene is hydrogenated.
- When the hydrogenated block copolymer is used for specific purposes, the above hydrogenated compound can be preferably used, as required, for the purposes.
- It is preferred that the amount of the polymer block A present in the component (a-1) is 5 to 70 % by weight, based on the weight of the component (a-1). Further, it is preferred that the total weight-average molecular weight of the component (a-1) is 50,000 to 550,000.
- The specific examples of the component (a-1) include styrene-ethylene/butene-styrene copolymer (SEBS), styrene-ethylene/propylene-styrene copolymer (SEPS), styrene-ethylene/ethylene/propylene-styrene copolymer (SEEPS), and styrene-butadiene/butylene-styrene copolymer (partially hydrogenated styrene-butadiene-styrene copolymer, SBBS).
- A number of methods have been proposed for producing the block copolymer, obtained by hydrogenating a block copolymer composed of at least 2 polymer blocks A mainly based on an aromatic vinyl compound and at least one polymer block B mainly based on a conjugated diene compound. One of the representative methods involves block polymerization effected in an inert medium in the presence of a lithium or Ziegler catalyst, as disclosed by Japanese Patent Publication No.S40-23798. The resultant block copolymer can be hydrogenated in an inert medium in the presence of a hydrogenation catalyst by a known method.
- The hydrogenated block copolymers of a conjugated diene compound useful for the present invention as the (a-2) component include a block copolymer (CEBC) composed of a crystalline ethylene block and non-crystalline ethylene-butene block obtained by hydrogenating a block copolymer of butadiene. The hydrogenated block copolymers of a conjugated diene compound may be used either individually or in combination.
- The non-aromatic-based softening agents for rubber as the component (b) for the thermoplastic elastomer composition of the present invention include a non-aromatic-based mineral oil, and liquid or low-molecular-weight synthetic agent. The softening agents of mineral oil for rubber are generally a mixture of an aromatic ring, naphthenic ring and paraffin chain compounds. They are distinguished from each other by the paraffin-, naphthene- and aromatic-based ones, when carbons in the paraffin chains account for 50% or more of the total carbons, those in the naphthene rings for 30 to 40%, and the aromatic ones for 30% or more, respectively.
- The softening agents of mineral oil for rubber useful as the component (b) for the present invention are paraffin- or naphthene-based ones. Use of an aromatic-based softening agent is undesirable, because it will make the component (a) soluble to retard the crosslinking reactions with the result that properties of the resultant composition may not be improved. The component (b) for the present invention is preferably a paraffin-based one, and the one having a lower aromatic ring content is more preferable. Examples of liquid or low-molecular-weight synthetic softening agents include a polybutene, a hydrogenated polybutene and a low-molecular-weight polyisobutylene. Among these, a polybutene and a hydrogenated polybutene are preferred.
- The non-aromatic-based softening agent for rubber preferably has a kinematic viscosity of 20 to 50,000cSt at 37.8°C and 5 to 1,500cSt at 100°C, pour point of -10 to -15°C, and flash point (COC) of 170 to 300°C. Moreover, it preferably has a weight-average molecular weight of 100 to 2,000.
- The component (b) is incorporated, when the component (a-1) is used as the component (a), at 30 to 150 parts by weight per 100 parts by weight of the component (a-1), preferably 50 to 120 parts by weight. At below 30 parts by weight, the resultant thermoplastic elastomer composition may have deteriorated moldability, excessively high hardness and deteriorated softness with the result that the composition may not give the rubber-touch product. At above 150 parts by weight, on the other hand, the resultant thermoplastic elastomer composition is liable to suffer bleed-out of the softening agent, and the formed article delamination and/or peeling of the components, deformation and flow marks on the surfaces.
- The component (b) is incorporated, when the component (a-2) is used as the component (a), at 30 to 170 parts by weight per 100 parts by weight of the component (a-2), preferably 50 to 160 parts by weight. At below 30 parts by weight, the resultant thermoplastic elastomer composition may have deteriorated moldability, excessively high hardness and deteriorated softness with the result that the composition may not give the rubber-touch product. At above 170 parts by weight, on the other hand, the resultant thermoplastic elastomer composition is liable to suffer bleed-out of the softening agent, and the formed article delamination and/or peeling of the components, deformation and flow marks on the surfaces.
- The petroleum hydrocarbon resin component (c) for the thermoplastic elastomer composition of the present invention has the effects of accelerating dispersion of the rubber in the resultant thermoplastic elastomer composition, improving outer appearances of the formed article, and adjusting hardness and shrinkage. Examples of such petroleum hydrocarbon resins include an aliphatic petroleum resin produced mainly from C5 fraction by-produced in the steam cracking of petroleum; an aromatic petroleum resin produced mainly from C9 fraction; and a C5C9 copolymer obtained by copolymerizing the above-mentioned C5 fraction with C9 fraction. There is no particular limitation with respect to the type of the petroleum hydrocarbon resin as long as the resin exhibits the below-mentioned softening point and melt viscosity. It is preferred that the petroleum hydrocarbon resin is a copolymer having aromatic groups.
- The component (c) has a softening point of 80 to 170°C, preferably 110 to 160°C. At a softening point of the component (c) out of the above range, the resultant elastomer composition may have deteriorated balances among softness, permanent compression set and moldability. Moreover, with respect to the component (c), the temperature at which the component (c) exhibits a melt viscosity of 10 poise is 120 to 250°C, preferably150 to 240°C. When this temperature is lower than 120°C, the resultant elastomer composition may have deteriorated rubber elasticity. When this temperature is higher than 250°C, the resultant elastomer composition may have deteriorated moldability.
- The preferable examples of commercially available resins usable as the component (c) include aromatic group-containing resins, such as Endex 155 (a copolymer produced using an aromatic monomer, Eastman Chemical) and Kristalex 5140 (a copolymer of α-methylstyrene with styrene, Eastman Chemical).
- The component (c) is incorporated at 3 to 100 parts by weight per 100 parts by weight of the component (a), preferably 10 to 50 parts by weight. At below 3 parts by weight, the resultant elastomer composition may have deteriorated moldability, and the formed article is liable to suffer delamination and/or peeling of the components, deformation and flow marks on the surfaces. At above 100 parts by weight, on the other hand, the resultant elastomer composition may also have deteriorated moldability, excessively high hardness and deteriorated softness with the result that the composition may not give the rubber-touch product.
- The thermoplastic elastomer composition of the present invention may be incorporated with the organic peroxide component (d), as required. The organic peroxide component (d) works to generate the radicals which are reacted with each other in a chain reaction manner to crosslink the component (a). Examples of compounds useful for the component (d) include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butyl peroxy)hexane, 2,5-dimethyl-2,5-di-(tert-butyl peroxy)hexyne-3, 1,3-bis(tert-butyl peroxyisopropyl)benzene, 1,1-bis(tert-butyl peroxy)-3,3,5-trimethyl cyclohexane, n-butyl-4,4-bis(tert-butyl peroxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide. Of these, 2,5-dimethyl-2,5-di-(tert-butyl peroxy)hexane and 2,5-dimethyl-2,5-di-(tert-butyl peroxy)hexyne-3 are particularly preferable for their characteristics related to odor, coloring and scorch safety.
- When it is used, the component (d) is incorporated at 0.01 to 3 parts by weight per 100 parts by weight of the component (a), preferably 0.05 to 1.0 parts by weight. At below 0.01 parts by weight, the resultant thermoplastic elastomer composition may have insufficient resistance to heat and mechanical strength, because of insufficient extent of crosslinking. At above 3 parts by weight, on the other hand, the resultant thermoplastic elastomer composition may have deteriorated moldability.
- The thermoplastic elastomer composition of the present invention may be incorporated with an ester-based crosslinking aid as the component (e), as required. The component (e) may be incorporated during the crosslinking step in the presence of the organic peroxide component(d) as the component (e) in the production of the thermoplastic elastomer composition, for the uniform and efficient crosslinking reactions. When used in a large quantity, it can adequately crosslink the non-aromatic-based softening agent for rubber, in particular low-molecular-weight paraffin-based oil or the like, to control its bleed-out from the thermoplastic elastomer composition.
- The compounds useful for the component (e) include multi-functional methacrylate compounds, e.g., triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate having 9 to 14 recurring units of ethylene glycol, trimethylol propane trimethacrylate, allylmethacrylate, 2-methyl-1,8-octanediol dimethacrylate and 1,9-nonanediol dimethacrylate; multi-functional acrylate compounds, e.g., polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate and propylene glycol diacrylate; and multi-functional vinyl compounds, e.g., vinyl butylate and vinyl stearate. They may be used either individually or in combination. Of these crosslinking aids, the multifunctional acrylate and methacrylate compounds are more preferable, and triethylene glycol dimethacrylate and tetraethylene glycol dimethacrylate are still more preferable. These compounds are easily handled, function to solubilize the organic peroxide and hence as the dispersion aid for the peroxide, and promote the uniform and efficient crosslinking reactions under heating, to give the thermoplastic elastomer composition of well-balanced hardness and rubber elasticity.
- The component (e) is incorporated, when it is used, preferably at 0.1 to 10 parts by weight per 100 parts by weight of the component (a), more preferably 0.1 to 3 parts by weight. At above 10 parts by weight, it may no longer exhibit its effect, because the resultant thermoplastic elastomer has a decreased extent of crosslinking due to the self-polymerization.
- The thermoplastic elastomer composition of the present invention may be incorporated with a peroxide-decomposed type polyolefin resin as the component (f), as required. The component (f) can significantly improve ability of thermal adhering of the formed article of the resultant thermoplastic elastomer with a formed article of peroxide-decomposed type polyolefin resin.
- The component (f) is composed of an olefin-based polymer or copolymer, thermally decomposed under heating in the presence of a peroxide to lose its molecular weight and have increased fluidity while being molten. The compounds useful for the component (f) include isotactic polypropylene or copolymer of propylene with another α-olefin compound, e.g., ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene or 1-octene.
- The homopolymer portion of the above olefin-based copolymer preferably has a DSC-determined melting point (Tm) of 150 to 167°C, and ΔHm of 25 to 83mJ/mg. Degree of crystallinity can be estimated from the DSC-determined Tm and ΔHm. The resultant thermoplastic elastomer composition may no longer exhibit improved resistance to oil and rubber elasticity at 100°C or higher, when the homopolymer portion has the Tm or ΔHm out of the above range.
- The component (f) preferably has a melt flow rate (MFR, determined at 230°C in accordance with ASTM D-1238) of 0.1 to 200g/10 minutes, more preferably 0.5 to 100g/10minutes. At an MFR below 0.1g/10 minutes, the resultant thermoplastic elastomer composition may have deteriorated moldability. At above 200g/10 minutes, on the other hand, it may have deteriorated rubber elasticity.
- The component (f) is incorporated, when it is used, preferably at 0.1 to 25 parts by weight per 100 parts by weight of the component (a), more preferably 1 to 20 parts by weight. At above 25 parts by weight, the resultant thermoplastic elastomer may have deteriorated softness and rubber elasticity.
- The thermoplastic elastomer composition of the present invention may be incorporated with one or more types of additives, in addition to the above-described components, as required. These additives include various types of blocking inhibitor, sealing improver, heat stabilizer, antioxidant, light stabilizer, ultraviolet ray absorber, lubricant, nucleating agent and colorant. Examples of antioxidants useful for the present invention include phenol-based ones, e.g., 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butyl phenol, 2,4-dimethyl-6-tert-butyl phenol, 4,4-dihydroxydiphenyl and tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane; phosphate-based ones; and thioether-based ones. Of these, phenol- and phosphate-based ones are particularly preferable. The antioxidant is incorporated preferably at 0 to 3.0 parts by weight per 100 parts by weight of the components (a) to (f) totaled, particularly preferably 0.1 to 1.0 parts by weight.
- The thermoplastic elastomer composition of the present invention can be produced by kneading the components (a) to (c), and, as required, optional components (d) to (g), which may be incorporated simultaneously or in an optional sequence.
- The melting/kneading method is not limited, and the known method may be used. For example, these components may be molten and kneaded by a single screw extruder, twin screw extruder, roll, Banbury mixer, or various types of kneader. The melting and kneading steps may be effected continuously by, e.g., a twin screw extruder of adequate L/D ratio, Banbury mixer or kneader. The preferable melt kneading temperature is 160 to 220°C.
- The thermoplastic elastomer composition of the present invention has adequate softness and permanent compression set, in particular excellent compression set at 70°C or lower, and causes no environmental pollution, because the formed article suffers only a limited extent of bleed-out of the softening agent even when exposed to an excessive stress-induced deformation or load.
- Therefore, the thermoplastic elastomer composition of the present invention can go into various areas, when formed into a shape, e.g., sealing parts for medical and food purposes, electric appliance parts, bottle cap packings, sealing parts for automobiles, and multi-color sealing parts formed with a polyolefin or hard thermoplastic elastomer. It is particularly useful for sealing parts of ink in a bubble jet printer or the like.
- The thermoplastic elastomer composition of the present invention is excellent in ability of thermal adhering with a polyolefin resin, in particular polypropylene-based resin. Therefore, the formed article of the thermoplastic elastomer composition can be easily thermal adhered with a formed article of polypropylene-based resin, to form the thermal adhesiveness composite article.
- The concrete examples of the thermal adhesiveness composite articles include sealing parts for medical and food purposes, electric appliance parts, bottle cap packings, sealing parts for automobiles, and multi-color sealing parts. The composite articles are particularly useful for sealing parts of ink in a bubble jet printer or the like.
- The present invention is described in more detail by EXAMPLES and COMPARATIVE EXAMPLES, which by no means limit the present invention.
- The properties of each composition were determined by the following methods.
- (1) Specific gravity: Specific gravity was determined in accordance with JIS K-7112 for the 1mm thick pressed sheet.
- (2) Hardness: Hardness was determined in accordance with JIS K-7215 for the 6.3mm thick pressed sheet using a durometer (hardness type A).
- (3) Tensile strength: Tensile strength was determined in accordance with JIS K-6301 for the 1mm thick pressed sheet punched into the No.3 dumb-bell shape at a tensile speed of 500mm/minute.
- (4) 100% elongation stress: 100% elongation stress was determined in accordance with JIS K-6301 for the 1mm thick pressed sheet punched into the No.3 dumb-bell shape at a tensile speed of 500mm/minute.
- (5) Breaking extension: Breaking extension was determined in accordance with JIS K-6301 for the 1mm thick pressed sheet punched into the No.3 dumb-bell shape at a tensile speed of 500mm/minute.
- (6) Permanent compression set: Permanent compression set was determined in accordance with JIS K-6262 for the 6.3mm thick pressed sheet after it was set at a deformation of 25% at 70°C for 22 hours.
- (7) Resistance to bleeding: The formed article was compressed at 25% at 70°C
for 168 hours, and visually observed for the bleeding and blooming of the
low-molecular-weight components, to determine its resistance to bleeding
according to the following standards:
- o ○: Very good
- ○: Good
- Δ: Slightly bad
- ×: Bad
- (8) Resistance to tacking: Two 1mm thick pressed sheets, described above,
were put one on another to prepare the test piece, which was kept under a
load of 500g/cm2 for 24 hours and visually observed for separated conditions
of the pressed sheets, to determine its resistance to tacking according to the
following standards:
- o ○: Very good
- ○: Good
- Δ: Slightly bad
- ×: Bad
- (9) Injection moldability: The 130 by 130 by 2mm injection-molded sheet was
visually observed for flow marks and sinks on the surfaces, to determine its
injection moldability according to the following standards:
- o ○: Very good
- ○: Good
- Δ: Slightly bad
- ×: Bad
- (10) Thermal adhering: The
test piece 1 shown in Figures 1 to 3 was tested by the 180 degree peel back strength test, to determine its peel back strength. -
- Referring to Figures 1 to 3, the
polypropylene resin plate 3, 150mm long, 25mm wide and 4mm thick, was prepared by injection molding under the following injection conditions. The resin for the test plate is described below.
Polypropylene resin: PP-BC8 (Japan Polychem), Degree of crystallinity: Tm 166°C, ΔHm: 82mJ/mg, MFR: 1.8g/10 minutes
(The injection molding conditions were those recommended by the resin maker)Injection molder FS-120 (Nissei Plastic Industrial) Forming temperature 180 to 220°C Mold temperature 40°C Injection speed 55mm/second Injection pressure 1,400kg/cm2 Dwelling pressure 400kg/cm2 Injection time 6 seconds Cooling time 45 seconds - The
paper 4 was put on part of thepolypropylene resin 3 by a double-faced tape. It was inserted in a mold, and the thermoplastic elastomer composition was injected into the mold under the following conditions, to prepare the test piece of thepolypropylene resin plate 3 and thermoplasticelastomer composition plate 2 thermal adhesiveness to each other at the area A.Injection molder FS-120 (Nissei Plastic Industrial) Forming temperature 180 to 220°C Mold temperature 40°C Injection speed 55mm/second Injection pressure 1,400kg/cm2 Dwelling pressure 0kg/cm2 Injection time 6 seconds Cooling time 45 seconds - The test piece thus prepared was tested by the 180 degree peel back strength test, where the thermoplastic
elastomer composition plate 2 was folded as shown in Figure 3, and the end of theplate 2 and that of theplate 3 were pulled in the arrowed directions, to determine the 180 degree peel back strength according to the following standards: - o ○: Breaking of the material
- Δ: Breaking at the interface
- ×: The plates separated from each other immediately after the test was started
-
- The composition components used in EXAMPLES and COMPARATIVE EXAMPLES are described below:
- (1) Hydrogenated block copolymer as the component (a-1; SEPS): SEPTON 4077 (Kuraray), Styrene content: 30% by weight, Number-average molecular weight: 260,000, Weight-average molecular weight: 320,000, Molecular weight distribution: 1.23, Degree of hydrogenation: 90% or more
- (2) Hydrogenated block copolymer of conjugated diene compound as the component (a-2; CEBC): DYNARON 6100P( JSR Corp.)
- (3) Paraffin oil as the component (b): PW 90 (Idemitsu Chemical), Number-average molecular weight: 980
- (4) Petroleum hydrocarbon resin as the component (c-1): Endex 155 (Eastman Chemical), Softening point: 151-155°C, Specific gravity: 1.05, Melt viscosity at 235°C: 10 poise
- (5) Petroleum hydrocarbon resin as the component (c-2): Kristalex 5140 (Eastman Chemical), Softening point: 137-143°C, Specific gravity: 1.07, Melt viscosity at 180°C: 10 poise
- (6) Organic peroxide as the component (d): PERHEXA-25B (NOF Corp.)
- (7) Crosslinking aid as the component (e): NK ESTER 3G (Shin-Nakamura Chemical)
- (8) Peroxide-decomposed type olefin-based resin as the component (f): PP-BC8 (Polypropylene (PP); Japan Polychem), Degree of crystallinity: Tm 166°C, ΔHm: 82mJ/mg, MFR: 1.8g/10 minutes
- (9) Antioxidant of hindered phenol/phosphate/lactone-based composite as the component (g): HP2215 (Ciba Speciality Chemicals)
-
- The components shown in Tables 1 to 4 were molten/kneaded into pellets by a twine screw extruder (L/D: 47) at 180°C and 350rpm as the screw speed. The resultant pellets were injection-molded to prepare the test pieces which were tested for various characteristics. The results are given in Tables 1 to 4.
- As shown in Table 1 and 2, each of the thermoplastic elastomer compositions prepared in EXAMPLES 1 to 8 was the composition of the present invention. It had good properties, whether or not it contained the optional components (d) to (g). The thermoplastic elastomer composition prepared in EXAMPLE 4 was particularly excellent in properties related to resealing and safety for medical equipment parts (Food Hygiene Act; standards for foods and additives (Notification No.370 of the Japanese Ministry of Health and Welfare issued in 1959), standards for tools and container wrappings of synthetic resin mainly composed of polystyrene (Notification No.20 of the Japanese Ministry of Health and Welfare issued in 1982)). The thermoplastic elastomer composition of the present invention, prepared by incorporating PP in the composition prepared in each of EXAMPLES 1 to 4 at 5 parts by weight per 100 parts by weight of SEPS, showed good ability of thermal adhering with a formed article of PP.
- The similarly good results were observed when the component (a-1) was replaced by DYNARON 6100P (JSR Corp.) as the component (a-2) hydrogenated block copolymer of conjugated diene compound. DYNARON 6100P (JSR Corp.) is a block copolymer (CEBC) composed of the crystalline ethylene block and non-crystalline ethylene-butene block, which is obtained by hydrogenating a block copolymer of butadiene. The composition prepared in each of EXAMPLES 5 to 8 contained PP and showed good thermal adhering with a formed article of PP.
- On the other hand, the composition prepared in each of COMPARATIVE EXAMPLES 1 to 2 and 9 to 10 contained the component (b) at a content out of the range for the present invention. When the component (b) was contained at a content below the range for the present invention, the resulting thermoplastic elastomer composition had an excessively high hardness, lost softness, could not give the product of rubber touch, and had deteriorated injection moldability. When the component (b) was contained at a content above the range, the resulting thermoplastic elastomer composition suffered notable bleeding, and had deteriorated resistance to tacking and deteriorated injection moldability (due to occurrence of remarkable gas burn mark, stick in mold and mold contamination). The composition prepared in each of COMPARATIVE EXAMPLES 3 to 4 and 11 to 12 contained the component (c-1) at a content out of the range for the present invention. When the component (c-1) was contained at a content below the range for the present invention, the resulting thermoplastic elastomer composition had deteriorated injection moldability. When the component (c-1) was contained at a content above the range, the resulting thermoplastic elastomer composition lost softness, and had deteriorated rubber elasticity and deteriorated injection moldability (due to occurrence of remarkable sink mark, flash and stringiness).
- The composition prepared in each of COMPARATIVE EXAMPLES 5 to 6 and 13 to 14 contained the component (b) at a content out of the range for the present invention. When the component (b) was contained at a content below the range for the present invention, the resulting thermoplastic elastomer composition had an excessively high hardness, lost softness, could not give the product of rubber touch, and had deteriorated injection moldability. When the component (b) was contained at a content above the range, the resulting thermoplastic elastomer composition suffered notable bleeding, had deteriorated degree of non-tackiness and injection moldability, and was insufficient in safety for medical equipment parts.
- The composition prepared in each of COMPARATIVE EXAMPLES 7 to 8 and 15 to 16 contained the component (c-1) at a content out of the range for the present invention. When the component (c-1) was contained at a content below the range for the present invention, the resulting thermoplastic elastomer composition had deteriorated injection moldability. When the component (c-1) was contained at a content above the range, the resulting thermoplastic elastomer composition lost softness, had deteriorated rubber elasticity and injection moldability, and was insufficient in safety for medical equipment parts.
- The thermoplastic elastomer composition of the present invention is controlled in bleed-out of the softening agent, excellent in softness, permanent compression set, and the formed article of the thermoplastic elastomer composition of the present invention causes no pollution of the ambient environments and can be used as excellent parts for various purposes, in particular it causes no deterioration of ink when used for the elastic part or the like for bubble jet printer, causes no deterioration of the content in a bottle when used for the bottle cap packing or the like, and causes no bleeding when used for the formed composite articles, e.g., multi-color sealing parts or the like formed with a polyolefin or hard thermoplastic elastomer, which articles are represented by the sealing parts for medical purposes, food purposes and electric appliances.
Claims (12)
- A thermoplastic elastomer composition containing:(a) 100 parts by weight of at least one hydrogenated block copolymer selected from the group consisting of:(a-1) a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of at least 2 polymer blocks A mainly based on an aromatic vinyl compound and at least one polymer block B mainly based on a conjugated diene compound, and(a-2) a hydrogenated block copolymer obtained by hydrogenating a block copolymer based on a conjugated diene compound;(b) 30 to 150 parts by weight of a non-aromatic-based softening agent for rubber; and(c) 3 to 100 parts by weight of a petroleum hydrocarbon resin having a softening point of 80 to 170°C, and a temperature at which said resin exhibits a melt viscosity of 10 poise is 120 to 250°C.
- The thermoplastic elastomer composition according to Claim 1, which further contains (d) 0.01 to 3 parts by weight of an organic peroxide.
- The thermoplastic elastomer composition according to Claim 2, which further contains (e) 0.1 to 10 parts by weight of an ester-based crosslinking aid.
- The thermoplastic elastomer composition according to Claim 1 or 2 or 3, which further contains (f) 0.1 to 25 parts by weight of a peroxide-decomposed type polyolefin resin.
- A formed article composed of the thermoplastic elastomer composition containing:(a) 100 parts by weight of at least one hydrogenated block copolymer selected from the group consisting of:(a-1) a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of at least 2 polymer blocks A mainly based on an aromatic vinyl compound and at least one polymer block B mainly based on a conjugated diene compound, and(a-2) a hydrogenated block copolymer obtained by hydrogenating a block copolymer based on a conjugated diene compound;(b) 30 to 150 parts by weight of a non-aromatic-based softening agent for rubber; and(c) 3 to 100 parts by weight of a petroleum hydrocarbon resin having a softening point of 80 to 170°C, and a temperature at which said resin exhibits a melt viscosity of 10 poise is 120 to 250°C.
- An elastic part composed of the formed article according to Claim 5 for medical, food or bubble jet printer purpose.
- A thermal adhesiveness formed composite article composed of the formed article according to Claim 5 and a formed article of polypropylene-based resin thermal adhered to each other under heating.
- An elastic part composed of the thermal adhesiveness formed article according to Claim 7 for medical, food or bubble jet printer purpose.
- A formed article composed of the thermoplastic elastomer composition containing:(a) 100 parts by weight of at least one hydrogenated block copolymer selected from the group consisting of:(a-1) a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of at least 2 polymer blocks A mainly based on an aromatic vinyl compound and at least one polymer block B mainly based on a conjugated diene compound, and(a-2) a hydrogenated block copolymer obtained by hydrogenating a block copolymer based on a conjugated diene compound;(b) 30 to 150 parts by weight of a non-aromatic-based softening agent for rubber;(c) 3 to 100 parts by weight of a petroleum hydrocarbon resin having a softening point of 80 to 170°C, and a temperature at which said resin exhibits a melt viscosity of 10 poise is 120 to 250°C;and(d) 0.01 to 3 parts by weight of an organic peroxide.
- An elastic part composed of the formed article according to Claim 9 for medical, food or bubble jet printer purpose.
- A thermal adhesiveness formed composite article composed of the formed article according to Claim 9 and a formed article of polypropylene-based resin thermal adhered to each other under heating.
- An elastic part composed of the thermal adhesiveness formed article according to Claim 11 for medical, food or bubble jet printer purpose.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001345649 | 2001-11-12 | ||
JP2001345649 | 2001-11-12 | ||
JP2002106621 | 2002-04-09 | ||
JP2002106621A JP3448582B2 (en) | 2001-11-12 | 2002-04-09 | Thermoplastic elastomer composition, molded product thereof and composite molded product |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1310524A1 true EP1310524A1 (en) | 2003-05-14 |
EP1310524B1 EP1310524B1 (en) | 2006-12-20 |
Family
ID=26624466
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02356169A Expired - Fee Related EP1310524B1 (en) | 2001-11-12 | 2002-09-02 | Thermoplastic elastomer composition, formed article of the same and composite formed article of the same |
Country Status (6)
Country | Link |
---|---|
US (1) | US6953824B2 (en) |
EP (1) | EP1310524B1 (en) |
JP (1) | JP3448582B2 (en) |
CN (1) | CN1204193C (en) |
DE (1) | DE60216879T2 (en) |
HK (1) | HK1055757A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1493794A1 (en) * | 2003-07-03 | 2005-01-05 | Collano AG | Adhesive composition |
US8829105B2 (en) | 2012-01-18 | 2014-09-09 | Eastman Chemical Company | Low molecular weight polystyrene resin and methods of making and using the same |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1474477B1 (en) * | 2002-02-11 | 2006-01-11 | DSM IP Assets B.V. | Thermoplastic elastomer composition |
JP4473094B2 (en) * | 2004-02-20 | 2010-06-02 | リケンテクノス株式会社 | Thermoplastic elastomer composition and thermoplastic resin composition using the same |
JP2005281489A (en) * | 2004-03-30 | 2005-10-13 | Riken Technos Corp | Thermoplastic elastomer composition |
JP2006131688A (en) * | 2004-11-02 | 2006-05-25 | Riken Technos Corp | Thermoplastic elastomer composition |
JP5502319B2 (en) * | 2006-02-13 | 2014-05-28 | 旭化成ケミカルズ株式会社 | Hydrogenated block copolymer, hydrogenated block copolymer-containing resin composition, cross-linked product and cross-linked foam thereof |
JP4974013B2 (en) * | 2009-07-28 | 2012-07-11 | トキワケミカル工業株式会社 | Extruded product with core material |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0770645A2 (en) * | 1995-10-27 | 1997-05-02 | Riken Vinyl Industry Co., Ltd. | Thermoplastic elastomeric resin composition and a process for the preparation thereof |
EP0810262A1 (en) * | 1996-05-28 | 1997-12-03 | Riken Vinyl Industry Co., Ltd. | Thermoplastic elastomeric resin composition and a process for the preparation thereof |
EP0845498A1 (en) * | 1996-11-29 | 1998-06-03 | Riken Vinyl Industry Co., Ltd. | Thermoplastic elastomeric resin composition and a process for the preparation thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4994508A (en) * | 1987-07-16 | 1991-02-19 | Asahi Kasei Kogyo Kabushiki Kaisha | Specific hydrogenated block copolymer composition and process for producing the same |
DE69032963T2 (en) * | 1989-05-19 | 1999-08-19 | Japan Synthetic Rubber Co Ltd | (Modified) hydrogenated diene block copolymer and composition containing the same |
CA2127575C (en) * | 1993-07-08 | 1999-07-06 | Yuichi Itoh | Olefin thermoplastic elastomer and laminate thereof |
JP3102844B2 (en) | 1995-11-28 | 2000-10-23 | 理研ビニル工業株式会社 | Thermoplastic elastomer resin composition and method for producing the composition |
JP2000000978A (en) | 1997-05-19 | 2000-01-07 | Bridgestone Corp | Ink tank, ink jet recorder and elastic member therefor |
-
2002
- 2002-04-09 JP JP2002106621A patent/JP3448582B2/en not_active Expired - Lifetime
- 2002-09-02 DE DE60216879T patent/DE60216879T2/en not_active Expired - Fee Related
- 2002-09-02 EP EP02356169A patent/EP1310524B1/en not_active Expired - Fee Related
- 2002-09-18 US US10/245,714 patent/US6953824B2/en not_active Expired - Lifetime
- 2002-09-26 CN CN02143441.7A patent/CN1204193C/en not_active Expired - Fee Related
-
2003
- 2003-10-06 HK HK03107172A patent/HK1055757A1/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0770645A2 (en) * | 1995-10-27 | 1997-05-02 | Riken Vinyl Industry Co., Ltd. | Thermoplastic elastomeric resin composition and a process for the preparation thereof |
EP0810262A1 (en) * | 1996-05-28 | 1997-12-03 | Riken Vinyl Industry Co., Ltd. | Thermoplastic elastomeric resin composition and a process for the preparation thereof |
EP0845498A1 (en) * | 1996-11-29 | 1998-06-03 | Riken Vinyl Industry Co., Ltd. | Thermoplastic elastomeric resin composition and a process for the preparation thereof |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1493794A1 (en) * | 2003-07-03 | 2005-01-05 | Collano AG | Adhesive composition |
WO2005003248A1 (en) * | 2003-07-03 | 2005-01-13 | Henkel Kgaa | Pressure-sensitive adhesive composition |
US7268178B2 (en) | 2003-07-03 | 2007-09-11 | Henkel Kommanditgesellschaft Auf Aktien | Pressure sensitive adhesive composition |
US8829105B2 (en) | 2012-01-18 | 2014-09-09 | Eastman Chemical Company | Low molecular weight polystyrene resin and methods of making and using the same |
US8946365B2 (en) | 2012-01-18 | 2015-02-03 | Eastman Chemical Company | Low molecular weight polystyrene resin and methods of making and using the same |
Also Published As
Publication number | Publication date |
---|---|
DE60216879T2 (en) | 2007-08-30 |
DE60216879D1 (en) | 2007-02-01 |
HK1055757A1 (en) | 2004-01-21 |
JP3448582B2 (en) | 2003-09-22 |
US6953824B2 (en) | 2005-10-11 |
JP2003206389A (en) | 2003-07-22 |
CN1418911A (en) | 2003-05-21 |
CN1204193C (en) | 2005-06-01 |
US20030105233A1 (en) | 2003-06-05 |
EP1310524B1 (en) | 2006-12-20 |
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